Combating acarids and insects with amido thiono phosphoric acid phenyl esters

ABSTRACT

(N-UNSUBSTITUTED AND N-MONO- AND N,N-DI-ALKYL-SUBSTITUTED AMIDO)-O-ALKYL-O-((2-CARBOALKOXY AND 2-CARBOCYCLOALKYOXY, I.E. 2-ALKOXY CARBONYL AND 2-CYCLOALKYOXY CARBONYL) PHENYL)-THIONO-PHOSPHORIC ACID ESTERS WHICH POSSESS ARTHROPODICIDAL, ESPECIALLY ACARICIDAL AND INSECTICIDAL, PROPERTIES AND WHICH MAY BE PRODUCED BY REACTING THE CORRESPONDING THIONOPHOSPHORIC ACID DIESTER MONOHALIDE WITH AMMONIA OR A PRIMARY OR A SECONDARY AMINE.

United States Patent 3,755,572 COMBATING ACARIDS AND INSECTS WITH AMIDO-THIONO-PHOSPHORIC ACID PHEN- YL ESTERS Gerhard Schrader, Wuppertal-Cronenberg, Ingeborg Hammann, Cologne, and Wilhelm Stendel, Wuppertal- Vohwinkel, Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany No Drawing. Original application Nov. 13, 1968, Ser. No. 775,540, now Patent No. 3,621,082. Divided and this application Apr. 15, 1971, Ser. No. 134,436 Claims priority, application Germany, Nov. 30, 1967, P 16 68 047.0 Int. Cl. A01n 9/36 US. Cl. 424-212 14 Claims ABSTRACT OF THE DISCLOSURE (N-unsubstituted and N-monoand N,N-di- -alkyl-substituted amido)-O-alkyl-O[(Z-carboalkoxy and 2-carbocycloalkyloxy, i.e. Z-alkoxy carbonyl and 2-cycloalkyloxy carbonyl) phenyl]-thiono-phosphoric acid esters which possess arthropodicidal, especially acaricidal and insecticidal, properties and which may be produced by reacting the corresponding thionophosphoric acid diester monohalide with ammonia or a primary or a secondary amine.

This application is a division of application Ser. No. 775,540, filed Nov. 13, 1968, now US. Pat. No. 3,621,082.

The present invention relates to and has for its objects the provision for particular new amido-thiono-phosphoric acid phenyl esters, i.e. (N-unsubstituted and N-monoand N,N-di- -a1kyl-substituted amido)-O-alkyl-O-[(2 carboalkoxy and 2-carbocycloalkyloxy, i.e. 2-alkoxy carbonyl and 2-cycloalkyloxy carbonyl) phenyl] -thionophosphoric acid esters, which possess arthropodicidal, especially insecticidal and acaricidal, properties, active compositions in the form of mixtures of such compounds With solid and liquid dispersible carrier vehicles, and methods for producing such compounds and for using such compounds in a new Way especially for combating pests, e.g. arthropods, with other and further objects becoming apparent from a study of the within specification and accompanying examples.

German Pat. 814,152 describes N,N-dirnethylamido-O- ethyl- (A) or bis-(N,N-dimethyl)-amido- (B) phosphoryl-salicylic acid ethyl esters which are obtainable by reaction of alkali metal salts of salicylic acid ester with the appropriate di-substituted phosphoric acid monochlorides. According to the information given in German Pat. 811,514, the aforesaid compounds are suitable for the active and passive control of sucking and eating insects. They are therefore usable as pesticides.

Furthermore, 0,0 dialkyl-thiono-phosphoryl-salicylic acid esters as well as their insecticidal and toxic effect are already known (R. L. Metcalf, Organic Insecticides (Interscience Publishers, New York, 1955) It has been found in accordance with the present invention that the particular new amido-thiono-phosphoric acid phenyl esters of the formula RO S N COOR "Ice exhibit strong arthropodicidal, especially insecticidal and acaricidal, properties.

The present invention also provides a process for the production of compounds of Formula I above in which an O-alkyl-thiono-phosphoric acid ester dihalide is reacted with a salicylic acid alkyl ester (or salt thereof) to form an O-alkyl-O-(Z carbalkoxy-phenyl)-thiono-phosphoric acid diester monohalide of the formula:

C 0 OR (Ila) in which R and R' are the same as defined above, and Hal is a halogen atom, preferably chloro or bromo, and the latter compound is then reacted with ammonia or a primary or secondary amine of the formula:

R; (II) in which R and R are the same as defined above.

Advantageously, the particular new compounds of Formula I are distinguished by outstanding insecticidal and acaricidal properties as well as, in some cases, extremely low toxicity to warm-blooded animals and concomitantly low phytotoxicity. The instant compounds possess a very strong activity against eating as well as sucking insects, and are in this respect superior to comparable known compounds of analogous constitution. The new compounds of the present invention therefore represent a genuine enrichment of the art.

The course of the two steps of the process of the invention is illustrated by the following reaction schemes:

(a) S Hal R0 8 HHal 1 9 R ()P P O 1 (g HaI O O R O O R (IIa (113") (Ila) R O\fi R 1 HH 1 H31 (I: R]

O O R (Ila) (111)) R O i N A) O O R in which the symbols R, R, R R and Hal are the same as defined above.

Advantageously, in accordance with the present invention, in the various formulae herein:

R represents straight and branched chain lower alkyl such as methyl to tert.-butyl inclusive, especially methyl, ethyl, nand iso-propyl, n-, isoand s-butyl, and the like, and more particularly alkyl having 14 or 1-3, and preferably 1-2, carbon atoms;

R represents straight and branched chain alkyl having 1-6 carbon atoms such as methlyl to tert.-butyl inclusive as defined above, amyl, n-hexyl, pinacolyl (i.e. [CH C-[CH ]CH), and the like, and more particularly alkyl having 2-6 or 2-5, and preferably, 2-4, carbon atoms, or 1-5, and preferably, 1-4, carbon atoms; or cycloalkyl having 5-6 ring carbon atoms such 3 as cyclopentyl and cyclohexyl, and preferably cyclohexyl;

R represents hydrogen; or lower alkyl such as methyl to tert.-butyl inclusive as defined above, and the like, and more particularly alkyl having 1-4 or 1-3 carbon atoms, preferably methyl and isopropyl; and

R represents hydrogen; or lower alkyl such as methyl to tert.-butyl inclusive as defined above, and the like, and more particularly alkyl having 1-4 or 13 carbon atoms, preferably methyl and isopropyl;

R and R being the same or dilferent when both are lower alkyl.

In particular, R is lower alkyl, especially C alkyl; R is C alkyl, especially C alkyl, or cyclohexyl; R is hydrogen or lower alkyl, especially C alkyl; and R is hydrogen or lower alkyl, especially C alkyl.

Preferably, R is C alkyl, R is C alkyl; R is hydrogen or C alkyl; and R is hydrogen or C alkyl.

The instant compounds particularly contemplate amide,- NC alkylamidoand N-C alkyl-N-C; alkylamido-O-C alkyl-O-[(2 carb-C alkoxy)phenyl]- thiono-phosphoric acid esters, especially where R is isopropyl.

The 0-alkyl-thiono-phosphoric acid ester dihalides and salicylic acid alkyl esters required as starting materials for the production process of the present invention are known from the literature and are readily available on an industrial scale. The same is true of the starting amines.

Both the first and the second step of the production process of the present invention are preferably carried out in the presence of a solvent (this term includes a mere diluent). As such, particularly suitable are water; low-boiling aliphatic alcohols, e.g. methanol, ethanol, propanol, butanol; ketones, e.g. acetone, methylethyl ketone, methylisopropyl ketone or methylisobutyl ketone; nitriles, e.g. acetonitrile and propionitrile; (optionally chlorinated) aliphatic or aromatic hydrocarbons, e.g. methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, mono-, diand tri chloroethylene, benzene, toluene, xylene, chlorobenzene; and others, e.g. diethyl ether, di-n-butyl ether or dioxan; and the like.

The first reaction step is preferably carried out in the presence of an acid-binding agent, while in the second step an excess of ammonia or primary or secondary amine serves advantageously as acid acceptor. Otherwise, alkali metal hydroxides, carbonates and alcoholates, such as potassium or sodium hydroxide, carbonate, methylate or ethylate, and also tertiary bases, such as triethylamine, diethylaniline or pyridine, and the like may be used for this purpose. Finally, it is also possible, instead of working in the presence of an acid-binding agent, to start from the appropriate salt, preferably an alkali metal salt or ammonium salt of the salicylic acid ester concerned.

The carrying out of the production process according to the present invention is possible within a fairly wide temperature range. In general, the work is carried out at room temperature or slightly to moderately elevated temperature, and preferably at substantially between about 20-60 C.

It has proved expedient, in both the first and second steps of the process, to continue stirring the reaction mixture (in each case, after combining the starting components) for a longer period (between 3 and 24 hours optionally with slight heating) in order to complete the reaction.

According to the Equations (a) and (b) given above, equimolar amounts of the starting materials are theoretically necessary. It has proved advantageous first to add the mixture of salicylic acid alkyl ester, acid acceptor and solvent (or the appropriate salt of the salicylic acid alkyl ester) to the O-alkyl-thiono-phosphoric acid 4 ester dichloride and, in the second step of the reaction, to add ammonia or the primary or secondary amine concerned to the O-alkyl-thiono-phosphoric acid ester monohalideif desired, dissolved in one of the aforesaid solvents; the reverse sequence may, however, also be followed.

Working up of the mixture may take place in each case in the usual manner by taking up the former in a waterimmiscible solvent, preferably a hydrocarbon or ether, washing the solution obtained, evaporating the solvent after separation of the layers and drying of the organic phase, and, if possible, subjecting the residue to fractional distillation.

The amido-thiono-phosphoric acid phenyl esters of the present invention are obtained either in the form of solid crystalline substances which can readily be further purified by recrystallization from the usual solvents or they are colorless to slightly colored, water-insoluble oils, some of which can be distilled under greatly reduced pressure without decomposition. When such distillation is not possible, the compounds can, however, be freed from the last volatile constituents by so-called slight distillation," that is, brief heating to slightly to moderately elevated temperature. In this way they can be purified.

As already stated above, the amido-thiono-phosphoric acid phenyl esters of the present invention possess an outstanding, rapidly-commencing and long-lasting insecticidal and acaricidal activity with, in some cases, extremely low toxicity to warm-blooded animals, and concomitantly slight phytotoxicity. The instant compounds are therefore usable with success in plant protection and the protection of stored products, as well as in the hygiene and veterinary medical fields, for the control of noxious sucking and biting insects, Diptera and mites.

To the sucking insects contemplated herein there belong, in the main, aphids (Aphidae) such as the green peach aphid (Myzus persicae), the bean aphid (D ralis fabae), the bird cherry aphid (Rhopalo-siphum padi.), the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), the currant gall aphid (Cryptomyzus korschelti), the mealy apple aphid (Sappaphis m'ali), the mealy plum aphid (Hyalopterus arundinis) and the cherry black-fly (Myzus cerasi); in addition, scales and mealybugs (Coccina), for example the oleander scale (Aspiaiotus hederae) and the soft scale (Lecanium hesperz'dznn) as well as the grape mealybug (Pseudococcus maritimum); thrips (Thysanoptera), such as Hereinathrips femoralis, and bugs, for example the beer bug (Piesma quadrata), the cotton bug (Dysdercus intermedius), the bed bug (Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bug (T riatoma infestans) and, further, cicadas, such as Euscelis bilobatus and Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all there should be mentioned butterfly caterpillars (Lepidoptera) such as the diamond-back moth (Plutella maculipennz's), the gipsy moth (Lymantria: dispar), the brown-tail moth (Euproctis chlysorrhoea) and tent caterpillar (Malacosoma neustria); further, the cabbage moth (Mamestra brassicae) and the cutworm (Agrotis segetum), the large white butterfly (Pierz's brassicae), the small winter moth (Cheimatobia brumata), the green oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygma frugiperda) and cotton Worm (Prodenia litura), the ermine moth (Hyponomeuta padella), the Mediterranean flour moth (Ephestia Kt'iniella) and greater wax moth (Galleria mellonella); and the like. Also to be classed with the biting insects contemplated herein are beetles (Coleoptera), for example the granary weevil (Sitophilus granarius=Calandra granaria), the Colorado beetle (Leptinotarsa decemlineata), the dock beetle (Gastrophysa viridula), the mustard beetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus), the raspberry beetle (Byrurus tomentosus), the bean weevil (Bruchidius=Acanth0scelides obtectus), the leather beetle (Dermestes frischi), the khapra beetle T rogoderma granarium), the flour beetle (Tribolium castaneum), the northern corn billbug (Calandra or Sitophilus zeamais), the drugstore vbettle (Stegobium paniceum), the yellow mealworm (Tenebrz'o molitor) and the sawtoothed grain beetle (Oryzaephilus surinamensis), but also species living in the soil, for example wireworms (Agriotes spec.) and larvae of the cockchafer (Melolontha melolontha); cockroaches, such as the German cockroach (Blatella germanica), American cockroach (Periplaneta americana), Madeira cockroach (Laucophaea or Rhyparobia madeirae), Oriental cockroach (Blatta orientalis), the giant cockroach (Blaberus giganteus) and the black giant cockroach (Blaberus fuscus) as Well as Henschou-tedenia flexivz'tta; further, Orthoptera, for example the house cricket (Acheta domestica); termites such as the eastern subterranean termite (Reticulitermes flavipes) and Hymenoptera such as ants, for example the garden ant (Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such as the vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly (Ceratitis capitata), the house fly (Musca domestica), the little house fly (Fannia canicularis), the black blow fly (Phormia aegina) and bluebottle fly (Callz'ph ra erythrocephala) as well as the stable fly (Stomoxys calcitrans); further, gnats, for example mosquitoes such as the yellow fever mosquito (Aedes aegypti), the northern house mosquito (Culex pipiens) and the malaria mosquito (Anopheles stephensi); and the like.

With the mites (Acari) contemplated herein there are classed, in particular, the spider mites (Tetranychidae) such as the two-spotted spider mite (T etranychus telarius=Tetranychus althaeae or Tetranychus wrticae) and the European red mite (Paratetranychus pilsus=Pan0- nychus ulmi), blister mites, for example the entrant blister mite (Eriophyes ribis) and :tarsonemids, for example the broad mite (Hemitarsonemus Iatus) and the cyclamen mite (Tarsonemus pallidus); finally, ticks, such as the relapsing fever tick (Ornithodorus moubata); and the like.

When used against hygiene pests and pests of stored products, particularly flies and gnats, the instant new active compounds are also distinguished by an outstanding residual activity on wood and clay, as well as a good stability to alkali on limed substrates.

In the veterinary medical field the new compounds of the present invention are usable with success against numerous noxious animal parasites (ectoparasites and endoparasites), such as arachnids, insects and worms; and the like.

As ectoparasites of animals as contemplated herein, there are mentioned from the class of the Arachnida: Ixodidae, as for example the cattle tick (Boophilus microplus) (strains normally sensitive to, and strains resistant to, phosphoric acid esters) and the sheep tick (Rhipicephalus bursa); Gamasidae, as for example the red birdmite (Dermanyssus gallinae); Sarcoptidae, as for example the cattle digging-mite (Sarcoptes bovis), the dog diggingmite (Sarcoptes canis), the sheep sucking-mite (Psoroptes ovis), the rabbit sucking-mite (Psoroptes cuniculi) and the mouse scab-mite (Myobia musculi); and the like.

As ectoparasites from the class of the insects as contemplated herein, there are mentioned. Mallophaga, as for example the dog hair-louse (Trichodectes canis), the cattle hair-louse (Damalinea bovis) and the hen featherlouse (Eom enacanthus stramineus); Anoplura, as for example the short-nosed cattle louse (Haematopinus eurysternus); Diptera, as for example the sheep ked (Melophagus ovz'nus) and Diptera larvae parasitic in warmblooded animals, as for example Lucilia sericata, Lucilia cuprina, Chrysomyia chloropyga and larvae of warbleflies, as for example the cattle warble-fly (Hypoderma bovis); Aphaniptera, as for example the dog flea (Ctenocephalides canis); and the like.

As endoparasites in animals as contemplated herein,

there are mentioned from the class of the nematodes: Strongylidae, as for example the nodule worm of sheep (Oesophagostomum columbianum); Ancylostomatidae, as for example the dog hock-warm (Uncinaria stenocephala) and the dog hook-worm Ancylostoma caninum; Ascarididae, as for example the dog ascarids (Toxocara canis and T oxascaris leonina); Trichostrongylidae, as for example the sheep abomasum-worm (Haemonchus contortus) and the worm of the small intestine of sheep (Trichostrongylus colubriformis); Trichuridae, as for exlample the hen hair-worm (Capillaria obsignata); and the ike.

The active compounds according to the instant invention can be utilized, if desired, in the form of the usual formulations or compositions with inert conventional pesticidal diluents or extenders, i.e. conventional pesticidal dispersible carrier vehicles such as solutions, emulsions, suspensions, emulsifia'ble concentrates, spray powders, pastes, soluble powders, dusting agents, granules, etc. These are prepared in known manner, for instance by extending the active compounds with conventional pesticidal dispersible liquid diluent carriers and/ or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g. conventional pesticidal surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents. The following may be chiefly considered for use as conventional carrier vehicles for this purpose: inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes, etc.), paraflins (e.g. petroleum fractions), chlorinated aliphatic hydrocarbons (e.g. methylene chloride, etc.), alcohols (e.g. methanol, ethanol, propanol, butanol, etc.), amines (e.g. ethanolamine, etc.), ethers, etheralcohols (e.g. glycol monomethyl ether, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides (e.g. dimethyl sulfoxide, etc.), ketones (e.g. acetone, etc.) and/or water; as well as inert dispersible finely divided solid carriers, such as ground natural minerals (e.g. kaolins, alumina, silica, chalk, i.e. calcium carbonate, talc, kieselguhr, etc.) and ground synthetic minerals (e.g. highly whereas the following may be chiefly considered for use as conventional carrier vehicle assistants, e.g. surface-acti-ve agents, for this purpose: emulsifying agents, such as non-ionic and/or anionic emulsifying agents (e.g. polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfonates, aryl sulfonates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other acaricides, insecticides, fungicides, herbicides, bactericides, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generally contemplate carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1-% by weight, and preferably 05-90% by weight, of the mixture, whereas carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is present in an amount substantially between about 0.0000l-20%, preferably 0.01-5 by weight of the mixture. Thus, the present invention contemplates over-all compositions which comprise mixtures of a conventional dispersible carrier vehicle such as (1) a dispersible inert finely divided carrier solid, and/ or (2) a dispersible carrier liquid such as an inert organic solvent and/or water preferably including a surface-active effective amount of a carrier vehicle assistant, e.g. a surface-active agent, such as an emulsifying agent and/or a dispersing agent, and an amount of the active compound which is effective for the purpose in question and which is generally between about 000001-9570, and preferably 0.0l-95%, by weight of the mixture.

The active compounds can also be used in accordance with the well known ultra-low-volume process with good success, i.e. by applying such compound if normally a liquid, or by applying a liquid composition containing the same, via very elfective atomizing equipment in finely divided for-m, e.g. average particle diameter of from 50- 100 microns, or even less, i.e. mist form, for example by airplane crop spraying techniques. Only up to at most about a few liters/hectare are needed, and often amounts only up to about 1 quart/acre, preferably 2-16 fluid ounces/acre, are sufiicient. In this process it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of active compound or even the 100% active substance alone, e.g. about 20-] 00% by weight of the active compound.

In particular, the present invention contemplates methods of selectively killing, combating or controlling pests, e.g. arthropods, i.e. insects and acarids, and more particularly, methods of combating at least one of insects and acarids which comprises applying to at least one of correspondingly (a) such insects, (b) such acarids, and (c) the corresponding habitat, i.e. the locus to the protected, a correspondingly combative or toxic amount, i.e. an arthropodicidally, especially insecticidally or acaricidally, efiective amount of the particular active compound of the invention alone or together with a carrier vehicle 8 as noted above. The instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, sprinkling, pouring, fumigating, and the like.

It will be realized, of course, that the concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon the intended application. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.

The unexpected superiority and outstanding activity of the particular new compounds of the present invention is illustrated without limitation by the following examples:

EXAMPLE 1 Phaedon larvae test Solvent: 3 parts by Weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol other To produce a suitable preparation of the particular active compound, 1 part by Weight of such active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier, and the resulting concentrate is diluted with water to the desired final concentration.

Cabbage leaves (Brassica oleracea) are sprayed with this preparation of the given active compound until dripping wet and then infested with mustard beetle larvae (Phaedon cochlearz'ae) After the period of time stated in the following table, the degree of destruction of the pests is determined and expressed as a percentage: 100% means that all and 0% means that none of the beetle larvae are killed.

The particular active compounds tested, their concentrations, the evalution time and the experimental results obtained can be seen from the following Table 1:

TABLE 1 Concentration Degree of doof 3023751 comstructionf in Active compound (constitution) poun ge rit t; 32:15;

(B) (CHmN O 0.1 O

H /P0 a) 2N C O- O C 2H5 (known comparative product) (A) C H O\f|) 0. 1 100 (known com parative product) manonn-o-Q (known comparative product) (11) O H O S 0.1 100 (2,) 011 0 S 0. 1 100 \%l O 00. 100 .001 95 N H:

C OO CaH'l-iSO (3 C2H50 S 0. 1 100 ll 0. 01 100 /PO O. 001 100 N H:

0 O-0 C H -iso TABLE 1Continued Concentration Degree of deof active comstruction in pound in perpercent aitcr Active compound (constitution) cent 3 days 41) CH O s 0.1 100 0.01 100 /PO 0.001 100 CH NH P (ho-003111450 CH S 0.1 100 (51) 2 50\" 0.0 100 /P-O 0.001 100 OH NH P 1O0C;H1-iso H 0 S 0.1 100 1) C: a \u 0 0.01 40 P- (CH) N/ 00-0 C3H7'i50 C H s 0.1 100 (7r).- 2 50\" 0.01 100 /P0 0.001 100 -C H NH a OOC H1-iso H 0 s 0.1 100 (81) C: s \H O 0.01 100 P- 6 NH: l

CO-OCzH -I1 0 H o s 0.1 100 5 0 0.01 100 NH: CO-OCH EXAMPLE 2 Cabbage plants (Brassica oleracea) which have been heavily infested with peach aphids (Myzus persicae) are Myzus test (Contact amen) sprayed with the preparation of the given active com- Solvent: 3 parts by weight acetone pound til dri in wet,

40 Emulslfiell 1 P y Welght y 'y P y y ether After the specified period of time, the degree of destruc- To produce a Suitable preparation of the particular a tion is determined as a percentage: 100%-means that all active compound 1 Part by weight of such active the aphids are kllled whereas 0% means that none of the pound is mixed with the stated amount of solvent conaphlds are klued' a r r The particular active compounds tested their concentaining the stated amount of emulsifier and the resultlng 45 concentrate is diluted with water to the desired final tratlons, the evaluation time and the results obtained can concentration be seen from the following Table 2:

TABLE 2 Conoentra- Degree of tion of destruction active in percent compound after Active compound (constitution) in percent 24 hours (B) (CH3)2N O 0.1 0

/P-O- 11cm (known comparative preparation) m C2H50\fi 0.1 o

(CH3) 2N l 0 O0 C2H5 (known comparative preparation) (C2H O)2PO 0 O0 C 2H (known comparative preparation) (1 C'zHsO S Oil 98 TABLE 2Continued Concentra- Degree of tion of destruction active in percent compound alter Active compound (constitution) in percent 24 hours (22) CHaO S 0.1 100 \II 0.01 93 P- NH2 C O-O Caliv-lso 3 C H 0 S 0.1 85 (2) 2 5 \l! 0.01 40 O O-O (33117-150 (7 CzHsO S 0.1 96

PO l G H N a 7- CO-OCzHr-isl) O H 0 S 0.1 100 (92) z r \H 0.01 30 /P0 CH 3 N 2 I CO-OCH CzHa EXAMPLE 3 of approximately -30 cm., are sprayed with the prep- Tetranychus test Solvent: 3 parts by weight acetone aration of the given active compound until dripping wet.

These bean plants are heavily infested with spider mites Emulsifier: 1 part by weight allrylaryl polyglycol ether To produce a suitable preparation of the active compound, 1 part by weight of such active comparticular pound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the resulting concentrate is diluted with water to the desired final concentration.

Bean plants (Phaseolus vulgaris), which have a height TABLE 3 Concentration of Degree of active destruction compound in percent Active compound (constitution) in percent after 8 days (B) (CH hN 0 0. 1 0

H /P-0- (CH MN I a o o-o 02H (known comparative preparation) (A) C3H50 O 0. 1 0

ll /PO C s)2N l 0 O0 C zHa (known comparative preparation) wnnohr-o-Q l t C 0-0 02115 (known comparative preparation) (2 (EH 0 S 0. 1 i1 o. 01 9o /P--0 NH:

C 0-0 CaHz-lSO (1;) (hHrO S 0. l 98 ll /P0 N H;

TABLE 3Continued Concentration of Degree oi active destruction compound in percent Active compound (constitution) in percent after 8 days (33) 011150 S i 0.1 100 \II 0.01 70 P-O NH:

C -0 G 3H7-iS0 (4;) CHaO S 0.1 98

\ll /P--0 CH;NH I

C 0-0 CaH7-iSO (7;) CaHtO S 0.1 100 /PO iSO-CsHr-NH CO-0 C3H7 iSO v P-O NH:

oo-o 03111-11 (9 C3H50 S 0.1 100 \H 0.01 70 /P--O- CH EXAMPLE 4 the given active compound. After immersion of, in each Tick test case, female specimens of the various species of ticks,

these are transferred to Petri dishes, the bottom of each of which is covered with a correspondingly large disc of filter paper.

7 After 10 days, the eifectiveness of the preparation of the given active compound is determined by ascertaining the inhibition of the depositing of eggs compared with untreated control ticks.

The effect is expressed as a percentage, 100% meaning that eggs ceased to be deposited and 0% signifying that the ticks deposited eggs in the normal amount.

The particular active compounds investigated, their concentrations, the para-sites tested and the findings obtained can be seen from the following Table 4:

W TABLE 4 Concentration of Inhibition active comof the depound in positing oi solution in eggs in Active compound (constitution) Parasite percent percent (B) (CHmN O Boophilus 1.0 mlcroplua 0. 3 50 PO 0. 1 50 Sensitive 0. 03 50 (C H N I 0. 01 0 C O O C2H5 0. 003 0 (known comparative preparation) (A) CzHsO 0 Bflophi l'llls 1. 0 50 I] microplus 0.3 50 P-O- 0. 1 50 Sensitive 0. 03 50 (CH3) 2N7 l o. 01 o C O O C2H5 0. 003 0 (known comparative'preparation) S Boophilus 1. 0 50 ll microplus 0. 3 50 (C2H50)2P'O 0.1 50 Sensitive 0. 03 50 0. 01 0 C O O C 2H5 0. 003 0 (known comparative preparation) (34) C2H5O S Boophilus 1. 0 ll microplua 0. 3 100 P-O 0. 1 100 Sensitive 0. 03 50 NH2 1 0.01 50 C O O CaHflso 0.003 50 TABLE 4-Continued Concentra- 'on Inhibition active comof the depound in positing of solution in eggs in Active compound (constitution) Parasite percent percent (74) 0 11 0 S Boophilus 1. 0 100 I] microplus 0. 3 100 P-O 0. 1 100 Sensitive 0. 03 100 iso-C H NH i 0. 01 100 O 0 0 C3H7l50 0. 003 100 0.001 50 (94) 0211 0 S Boophilus 1.0 100 ll microplus 0. 3 r. 100 PO 0.1 100 Sensmve 0. 03 50 C O O CH-C Ha 2; 03 0 s Boophilus 1. 0 100 11 mzcroplua 0. 3 50 P-O 01 50 Sensitive 0.03 50 NH: l

COOCsHuSO EXAMPLE 5 mg concentrate is diluted with water to the deslred final Test with parasitic fly larvae To produce a suitable preparation of the particular active compound, parts by weight of such active compound is mixed with the stated amount of solvent which contains the stated amount of emulsifier, and the resultconcentration.

About 20 fly larvae (Chrysomyia chloropyga) are brought into a test-tube which contains about 2 cc. of horse muscle. Onto this horseflesh are brought 0.5 ml. of the above preparation of the given active compound. After 24 hours, the degree of destruction is determined as a percentage. 100% means that all, and 0% that no, larvae were killed.

The particular active compounds investigated, their concentrations and the findings obtained can be seen from the following Table 5:

TABLE 5 Concentration of active compound Degree 01' in solution destruction Active compound (constitution) Parasite in percent in percent (B) (CHmN 0 Chrysomuio 0. 03 o ll chloropyaa 0. 01 0 P-O 0. 003 0 (0 Ha) 0. 001 0 C O O C 2 5 (known comparative preparation) (A) CaHrO O Chrysomyia 0. 03 0 II chloropyga 0. 01 0 P-O 0. 003 0 0. 001 0 0 a) 2N C 0 O 0 2H,

(known comparative preparation) (C) S Chrwomm'a 0. 03 .0 il chloropwa 0. 01 0 zHs )rP0 0. 003 o 0. 001 0 (known comparative preparation) (3 C2H5D S Chrysomyia 0. .03 100 ll chloropyqa 0. 003 100 P-O- 0. 0003 0. 00003 0 NH;

O 0 0 O -,H-1iso (1 CzHsO S V Chrysomyia 0. 03 H chluromau 0. 003 50 PO 0. 0003 0 Ng TABLE 5-Contlnued Concentration of active compound Degree of in solution destruction Active compound (constitution) Parasite in percent in percent (2 CH S Chryaomyiu 0. 03 100 [I chloropyga 0. 003 100 P() 0. 0003 50 N Ha I C O O C 3H -iso (7 C2H5O S Chrysomyia 0. 03 100 H chloropyga 0. 003 100 P-O 0003 50 0 00003 0 iso-CaH N I C O O C3H7-1SO The process of the invention is illustrated by the following examples:

EXAMPLE 6 CgHsO S 2 ooomnnm on (a) l-molar mixture: To 180 g. ethyl-thiono-phosphoric acid ester dichloride there are added at 40 to 50 C., with stirring, a mixture of 136 g. salicylic acid isopropyl ester, 220 g. water and 24 g. sodium hydroxide; the reaction mixture is then stirred for 4 hours and it is then taken up in 400 ml. benzene. The benzene solution is washed twice with water, dried over sodium sulfate and, finally, the product is fractionally distilled. 155 g. O-ethyl O [(Z-carbo-isopropoxy)phenyl]-thiono-phosphoric acid diester monochloride of B.P. 120/0.01 mm. Hg are obtained.

(b) 0.2-molar mixture: 66 g. (0.2 mol) of the O-ethyl- 0-[(2-carbo-isoprop0xy)phenyl] -thiono phosphoric acid diester monochloride prepared according to (a) are added, with stirring, to 90 ml. of ammonia solution. The temperature of the solution rises gradually to to 60 C. After subsidence of the exothermic reaction, the mixture is stirred for a further 24 hours at room temperature. The reaction mixture is then taken up in 200 ml. benzene, the benzene solution is washed with water until it has a neutral reaction, then dried over sodium sulfate, and the solvent is removed under reduced pressure. 46 g. (76% of the theory) of the amido-thiono-phosphoric acid O-ethyl-0-[(Z-carbo-isopropoxy)phenyl] ester are obtained in the form of a colorless, water-insoluble oil.

Analysis.Calcd. for C H NO PS (molecular weight 303) (percent): P, 10.2; N, 4.6. Found (percent): P, 9.9; N, 4.3.

The median toxicity of the compound in the rat per os is 1000 mg./ kg.

EXAMPLE 7 CHaO S (a) The O-methyl O [(2-carbo-isopropoxy)phenyl]- thiono-phosphoric acid diester monochloride required as intermediate product is prepared in manner analogous with the corresponding O-ethyl compound [cf. Example 6(a)]. The substance is obtained in the form of a nondistillable oil. The yield is 60% of the theory.

ArnalysisP-Calcd. for C H ClO PS (molecular weight 308.5) (percent): P, 10.0; S, 10.4. Found (percent): P, 9.4; S, 9.7.

(b) Preparation takes place by a method analogous to that of Example 6(b). The amido-thiono-phosphoric acid O-methyl-O-[(2-carbo-isopropoxy)phenyl] ester, after recrysgallization from a ligroin-ethyl acetate mixture, melts at C.

Analysis.Calcd. for C H NO PS (molecular weight 289) (percent): P, 10.7; 'S, 11.1; N, 4.8. Found (percent):

P, 10.7; S, 1101; N, 4.8.

EXAMPLE 8 l o NH CH3 1 50-55% (a) In manner analogous with that described in Example 6(a), the 0-ethyl-0-[(2-carbo-sec.-butoxy)phenyl1- thionophosphoric acid diester monochloride is obtained as non-distillable oil with a yield of 82% of the theory.

Analysis.--Calcd. for C H ClO PS (molecular weight 336.5) (percent): P, 9.2; S, 9.5. Found (percent): P, 9.0; S, 9.3.

(b) By reaction of O-ethyl-O -[2-carbo-sec.-butoxy) phenyl]-thiono-phosphoric acid diester monochloride with ammonia according to Example 6(b), the amido-thionophosphoric acid O-ethyl-O-[(2-carbo-sec.-butoxy)phenyl] ester is obtained in a yield of 99% of the theory.

Analysis.-Calcd. for C H NO PS (molecular weight 317.5): P, 9.8%. Found: P, 9.3%.

EXAMPLE 9- is0CaH1NE I To a solution of 162 g. (0.5 mol) O-ethyl-O-[(2-carboisopropoxy)phenyl]-thiono-phosphoric acid diester monochloride (prepared according to Example 6(a) in 600 ml. benzene there are added, at 20 to 40 C., 75 g. isopropylamine dissolved in 75 ml. benzene. After subsequent stirring of the reaction mixture for one hour, it is extracted with water, the benzene phase is separated, dried, and evaporated, and the residue is fractionally distilled. The N-isopropylamido-thiono-phosphoric acid O-ethyl-O-[(2- cube-isopropoxy)phenyl] ester boils at C. under a pressure of 0.01 mm. Hg. The yield is g. (82% of the theory).

Analysis.-Calcd. for C H NO PS (molecular weight 345) (percent): P, 9.0; S, 9.3; N, 4.1. Found (percent): P, 9.2; S, 9.7; N, 4.2.

In analogous manner, the following compounds can be obtained:

20 described in Example 6(b) with a yield of 62% of the theory.

Percent Yield, Calculated Found percent of Empirical Molecular- Constitution the theory formula weight P S N P S N (5 CzHsO S 74 CtaHzoNOrPS 317 4.4 3.6

\N /PO GHr-NH COOCgHziSO (62)- CzH O S 76 CuHz2NO4PS 331 9.4 9.7 4.2 9.9 10.4 4.4

\l! /PO sh COOCsHflSO (4 01-1 S 4.6 CraHlsNOiPS 303 4.6 3.9

\H /PO CHz-NH OOCgHriSO EXAMPLE l0 Analysis-Gabi for C H NO PS (molecular weight 02350 S 303) (perent): P, 10.2; S, 10.5. Found (percent): P,

25 9.7; S, 10.0. EXAMPLE 12 HzN A;

OOCgH5 5) CgH5O S (a) 1 mol of spdium methylate is added to 166 g. (1 mol) salicylic acid ethyl ester in 300 ml. methanol and the solution is concentrated by evaporation. The residue is added, at 20 to 35 C., to 180 g. O-ethyl-thiono-phosphoric acid ester dichloride in 1000 ml. methylethyl ketone; the mixture is then stirred overnight, benzene is added to it, it is extracted with water, and the organic phase is separated, dried and evaporated. There are obtained in this way 220 g. (71% of the theory) of O- ethyl O [(2 carboethoxy)phenyl]-thiono-phosphoric acid diester monochloride of B.P. 110 C./0.01 mm. Hg.

Analysis.Calcd. for C H CIO PS (molecular weight 308.5) (percent): P, 10.0; S, 10.4; C1, 11.5. Found (percent): P, 10.7; S, 10.8; C1, 11.7.

(b) 93 g. (0.3 mol) of the 0-ethyl-O-[(2 carboethoxy)phenyl]-thiono-phosphoric acid diester monochloride prepared according to (a) are dissolved in 300 ml. ethylene chloride, and ammonia is introduced into this solution at to 50 C. until cessation of the exothermic reaction. The mixture is then washed with 100 ml. water, the organic phase is dried and evaporated, and the residue is recrystallized from petroleum ether. The yield is 55 g. (63% of the theory). The amido-thionophosphoric acid 0 ethyl O [(2 carbo ethoxy) phenyl] ester melts at 42 C.

Analysis.-Calcd. for C H NO PS (molecular weight 289) (percent): P, 10.7; S, 11.1; N, 4.8. Found (percent): P, 10.8; S, 11.1; N, 4.5.

EXAMPLE l1 (a) Preparation of the O-ethyl O [(2 carbo-npropoxy)phenyl]-thiono-phosphoric acid diester monochloride is effected in a manner analogous to that of Example 6(a) for the corresponding isopropyl compound. The product is obtained in the form of a nondistillable oil. The yield is 55% of the theory.

Analysis.-Calcd. for C H ClO PS (molecular weight 322.5) (percent): P, 9.6; S, 9.9. Found (percent): P, 9.3; S, 9.2.

(b) The amido-thiono-phosphoric acid 0-ethyl-O-[(2- carbo-n-propoxy)phenyl] ester is obtained in the manner (a) A mixture of 33 g. sodium hydroxide, 200 ml. water and 165 g. salicylic acid cyclohexyl ester is added, at 20 to 30 C., to 135 g. (0.75 mol) O-ethyl-thionophosphoric acid ester dichloride. The reaction mixture is subsequently stirred for a further 3 hours, then taken up in ether, the etheral solution is dried, the solvent is evaporated and the O-ethyl O [(2-carbo-cyclohexoxy) phenyl]-thiono-phosphoric acid diester monochloride remaining behind as residue is slightly distilled.

Analysis.-Calcd. for C H ClO PS (molecular Weight 362.5) (percent): P, 8.5; S, 8.8. Found (percent): P, 8.2; S, 8.3.

(b) 145 g. (0.4 mol) of O-ethyl O [(2 carbo-cyclohexoxy)phenyl]-thiono-phosphoric acid diester monochloride [prepared as described under l2(a)] are stirred together with ml. ammonia solution overnight. The reaction mixture is then taken up in ether, the ethereal solution is dried, the solvent is evaporated, and the residue is slightly distilled.

The yield of amido-thiono-phosphoric acid O-ethyl-O- [(2 carbo-cyclohexoxy)phenyl] ester is g. (84% of the theory).

Analysis.Calcd. for C H NO PS (molecular weight 343) (percent): P, 9.0; S, 9.3; N, 4.1. Found (percent): P, 8.9; S, 9.1; N, 3.8.

It will be realized that all of the foregoing compounds contemplated by the present invention possess the desired selective pesticidal, especially arthropodicidal, i.e. insecticidal or acaricidal, properties for combating insects and acarids, and that such compounds have not only a very slight toxicity toward warm-blooded creatures, but also a concomitantly low phytotoxicity.

As may be used herein, the terms arthropod, arthropodicidal and arthropodicide contemplate specifically both insects and acarids. Thus, the insects and acarids may be considered herein collectively as arthropods to be combated in accordance with the invention, and accordingly the insecticidal and/or acaricidal activity may be termed arthropodicidal activity, and the concomitant combative or effective amount used will be an arthropodicidally eflective amount which in effect means an 21 insecticidally or acaricidally etfective amount of the active compound for the desired purposes.

It will be appreciated that the instant specification and examples are set forth by way of illustration and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention.

What is claimed is:

1. A method of combating acarids and insects which comprises applying to an acarid, insect or habitat thereof an acaricidally or insecticidally effective amount of a compound of the formula R P t 500R R2 in which R is lower alkyl,

R is selected from the group consisting of alkyl having 1-6 carbon atoms and cycloalkyl having -6 carbon atoms,

R is selected from the group consisting of hydrogen and lower alkyl, and

R is selected from the group consisting of hydrogen and lower alkyl.

2. The method of claim 1, wherein R is C alkyl, R is selected from the group consisting of C alkyl and cyclohexyl, R is selected from the group consisting of hydrogen and C alkyl, and R is selected from the group consisting of hydrogen and C; alkyl.

3. The method of claim 1 wherein said compound is amido-O-ethyl-O-[ (2 carbo-ethoxy)phenyl1-thiono-phosphoric acid ester of the formula (Bo-0cm,

4. The method of claim 1 wherein said compound is amido O methyl-O-[ (2-carbo-isopropoxy)phenyl]-thiono-phosphoric acid ester of the formula CHsO S 5. The method of claim 1 wherein said compound is amido O ethyl-O-[(2-carbo-isopropoxy)phenyl]-thiono-phosphoric acid ester of the formula 6. The method of claim 1 wherein said compound is N-methyl-amido O methyl O [(2-carbo-isopropoxy) C 0-0 CaHHSO 7. The method of claim 1 wherein said compound is N-methyl-amido 0 ethyl-O-[(2-carbo-isopropoxy)phenyl]-thiono-phosphoric acid ester of the formula CHPNH C 0-0 C301-iso 8. The method of claim 1 wherein said compound is N,N-dimethyl-amido O ethyl-O-[(Z-carbo-isopropoxy) phenyl]-thiono phosphoric acid ester of the formula C2H5O a)zN C 0-0 CaH .iso

9. The method of claim 1 wherein said compound is N-isopropyl-amido-O-ethyl-O- (2-carbo-isopropoxy) phenyl]-thiono-phosphoric acid ester of the formula ozmo s 114, lSO-CaHr-NH 10. The method of claim 1 wherein said compound is amido O ethyl-O-[(Z-carbo-n-propoxy)phenyl]-thionophosphoric acid ester of the formula CgH O S lLo co-o CaH -n 11. The method of claim 1 wherein said compound is amido O ethyl-O-[(2-carbo-isobutoxy)phenyl] -thion0- phosphoric acid ester of the formula on, n N 2 oo-oo 12. The method of claim 1 wherein said compound is amido O ethyl O [(Z-carbo-cyclohexyloxy)phenyl]- thiono-phosphoric acid ester of the formula '13. An acaricidal and insecticidal composition containing an acaricidally or insecticidally effective amount of a compound of the formula R0 P R1 ii-O o o R in which R is lower alkyl,

R is selected from the group consisting of alkyl having 1-6 carbon atoms and cycloalkyl having 5-6 carbon atoms,

R is selected from the group consisting of hydrogen and lower alkyl, and

R is selected from the group consisting of hydrogen and lower alkyl,

in admixture with a solid diluent or in admixture with a liquid diluent containing a surface-active agent.

14. The composition of claim 13 wherein said compound is:

23 N,N-dimethyl-amido-O-ethyl-O- (Z-carbo-isopropoxy) phenyH-thiono-phosphoric acid ester, N-isopropyI-amido-O-ethyl-O- Z-carbo-isopropoxy) phenyH-thiono-phosphoric acid ester, amido-O-ethy1-O-[ (2-carbo-n-propoxy)pheny1]-thionophosphoric acid ester, amido-O-ethyl-O- 2-carbo-isobutoxy phenyl] -thion0- phosphoric acid ester, or amido-O-ethyl-O-[ (Z-carbo-cyclohexyloxy pheny1]- thiono-phosphoric acid ester.

References Cited UNITED STATES PATENTS 3,621,082 11/1971 Schrader et a1 260941 2,831,014 4/1958 Sallmann et a1 260-941 3,121,105 2/ 1964 McConnell et a1 260941 ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner $32353? UNITED STATES PA'LENT ormct 'i CERTIFICATE 9F CQRREC'HON latent No. 3 755 572 I Dated Augll st ZBJ 1973 I i Gerhard Schrader et al I It is certified that error appears in the above-identified patent iand that said Letters Patent are hereby corrected as shown below:

Ccl. 2, line 22 change (In to (Ilb) a I: Col. 20, line 24 correct spelling of (perczenfi first occurrenc Col. 20, line 40, correct spelling of "ethereal".

Col. 21, line 74, claim 7, in the structural formula, change u n I 06 0 180 to C0 063 1-1 1S0 'Col. 22, line 46, claim 13, in the structural formula, change llPll t S Signed and sealed this 8th day of October 1974.

(SEAL) Attest:

McCOY M. GIBSONJR. c. MARseALL DANN .Attesting Officer Commissioner of Patents 

